Silver halide photosensitive material

ABSTRACT

A silver halide photographic light sensitive material comprising a transparent support and provided thereon a light sensitive layer containing a yellow coupler, a magenta coupler and a cyan coupler to form a monochromatic image upon color development after exposure, wherein a relative coupling rate of the magenta coupler with an oxidation product of a color developing agent is higher than that of the yellow or cyan coupler.

FIELD OF THE INVENTION

The present invention relates to a silver halide photographic lightsensitive material forming a monochromatic image, and in particular, toa silver halide photographic light sensitive material (hereinafter,referred to as a photographic material) for use in picture-taking, whichis color developable.

BACKGROUND OF THE INVENTION

Currently, there has been widely spread a photographic system in which acolor photographic material for picture-taking (color negative film) isloaded into a camera, exposed, developed, and the developed colornegative is printed on color print paper to obtain a color positiveimage (negative-positive system).

On the other hand, a reversal-type color photographic material forpicture-taking (color reversal film), after exposed, is subjected onlyto reversal development to obtain a positive image, having advantagesthat the developed film is observed as it is or through a slideprojector, or is printed to produce a positive color print(positive-positive system). However, the reversal photographic materialis not as popular as the negative-positive system described above,because the photographic material is not suited for easy photographingbecause of narrow photographic latitude, and positive color prints arerather expensive.

Recently, there appeared in the market a prepackaged photographic unit,so-called lens-fitted film in which unexposed color negative film ispackaged in the state ready for immediate exposure, leading to anincrease of picture-taking opptunities to further promote thenegative-positive system.

Along with the spread of the color photographic system, recently,black-and-white (or monochromatic) photographic camera material caused asmall boom. This was contemplated to be due to the fact thatblack-and-white (or monochromatic) images are freshly appreciated andits unique portrayal is considered mysterious, compared to the commonflooded color photographs.

The main users of conventional monochromatic photographic cameramaterials were primarily professionals and advanced amateurs. However,since "Torikkiri Konica Shirokuro" (Film-In-Mini Konica Black-and-White)was put on the market in April, 1995, everybody was allowed to enjoybasic photography using monochromatic photographic materials. As aresult, the photographic industry could not help but direct itsattention to be directed to this unexpectedly popular medium.

Silver image forming-type monochromatic photographic camera materialsare entirely different in photographic processing from colorphotographic system of negative-positive process, producing problemssuch that troublesome selection and handling of monochromaticphotographic materials was needed in the commercial processingfacilities and a separate processing line for monochromatic photographicmaterials had to be installed.

There are known monochromatic photographic camera materials which arecompatible with broadly popularized color photographic processing of thenegative-positive system; for example, a monochromatic image formingphotographic material by the use of a black coupler, as disclosed inU.S. Pat. Nos. 2,592,514 and 4,348,474; JP-B 63-59136 (herein, the term"JP-B" refers to examined and published Japanese Patent). U.S. Pat. Nos.2,181,944, 2,186,736, 4,368,255 and 5,141,844; JP-A-57-56838,57-5814758-215645, 3-107144, 6-214357 and 7-199421; and JP-A 6-505580also disclose a technique of forming monochromatic dye image by using amixture of yellow, magenta and cyan couplers.

Although processed in common with conventional processing, any of thesehad the problem that printing on print paper was troublesome. When theabove-described technique is applied to conventional color development,either one of color forming components destroys, due to difference inreactivity of the couplers, the balance with other components. As aresult, it becomes difficult to obtain neutral gray color in the overalldensity range or processing variation due to the concentration of adeveloping agent, pH, temperature or contamination (carrying-in ofundesired material), making it difficult to stably form monochromaticimages. Preferred as monochromatic prints in final image, are warm colortone, warm, nostalgic sepia color tone, therefore, easy making of thesesepia-toned monochromatic prints is desired.

Further, even if monochromatic images can be formed in color negativedevelopment by combination with color print paper, and unlessmonochromatic paper printing suitability is provided, it is verydifficult to respond to broad consumer needs.

In the case of forming monochromatic images with dyes, all of thecouplers react in a high exposure region to cause nongranularity,leading to superior graininess in the high density region, as comparedto a silver image. However, graininess in a low exposure region, on thecontrary, is deteriorated, so that it is necessary to enhance graininessof monochromatic dye images in the low exposure region. Since the humaneye is very sensitive to even slight color shift from neutral monotone,it is further necessary to design so as to produce a smooth tone, takingaccount of dependence of development and balance of developability withrespect to high-sensitive, medium-sensitive and low-sensitive layers.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide amonochromatic image forming silver halide photographic light sensitivematerial for picture-taking use, which is suited for color photographicprocessing of the negative-positive system, is superior in graininess,is easy to print on color or black-and-white paper and is capable ofeasily producing a sepia-toned black-and-white print.

The object of the present invention was accomplished by the following:

(1) a silver halide photographic light sensitive material comprising atransparent support and provided thereon a light sensitive layercontaining a yellow coupler, a magenta coupler and a cyan coupler toform a monochromatic image upon color development after exposure,wherein a relative rate of coupling of the magenta coupler with anoxidation product of a color developing agent is higher than that of theyellow or cyan coupler;

(2) the silver halide photographic material described in (1), whereinthe relative coupling rate of the yellow, magenta or cyan coupler isdefined in term of the following CRR value, the CRR value of the magentacoupler being less than that of the yellow or cyan coupler,

    CRR=(Do).sub.max /(Dc).sub.max

wherein (Do)_(max) represents a maximum density obtained when aphotographic material sample that contains indivisually the yellow,magenta or cyan coupler is subjected to exposure and color developmentin a developing solution, and (Dc)_(max) represents a maximum densityobtained when the photographic material sample is subjected to exposureand development in the developing solution that further containscitrazinic acid of 1.5 g/l;

(3) the silver halide photographic material described in (1) or (2),wherein a CRR value of the magenta coupler (CRR-M), that of the yellowcoupler (CRR-Y) and that of the cyan coupler (CRR-C) satisfy thefollowing relationship,

    0.8<CRR-M/CRR-Y<1.0

    0.8<CRR-M/CRR-C<1.0;

(4) the silver halide photographic material described in (1), (2) or(3), wherein the yellow, magenta and cyan couplers are represented bythe following formulas (1), (2) and (3), respectively, ##STR1## whereinR₁ and R₂ each represent a hydrogen atom or a substituent, k and l eachrepresent an integer of 1 to 5, provided that when k or l is 2 or more,plural R₁ s or plural R₂ s may be the same with or different from eachother and X represents a group capable of being released upon couplingwith an oxidation product of an aromatic primary amine color developingagent, ##STR2## wherein R₃ represents a substituent, R₂ and l each arethe same as defined in formula (1), provided that when l is 2 or more,plural R₂ s may be the same with or different from each other, and Xrepresents a group as defined in formula (1), provided that the group isbonded, through a nitrogen atom, to the 4-position of a pyrazolone ring,##STR3## wherein R₂ and R₃ are the same as defined in formula (2), prepresents an integer of 1 to 4, provided that when p is 2 or more,plural R₂ s may be the same with or different from each other, and X isa hydrogen atom or the same as defined in formula (1);

(5) the silver halide photographic material described in (1), (2) or(3), wherein the yellow and cyan couplers are those represented byformula (1) and (3), respectively, and the cyan coupler is a polymercoupler obtained by polymerizing a monomer represented by the followingformula (4), ##STR4## wherein R₂ and l are the same as defined informula (2), provided that when l is 2 or more, R₂ may be the same withor different from each other, X is the same as defined in formula (1)and Q represents a substituent having an ethylenic unsaturated doublebond;

(6) the silver halide photographic material described in (1), (2) or(3), wherein the yellow, magenta and cyan couplers are those representedby the following formulas (5), (6) and (7), respectively, ##STR5##wherein R₁ represents a hydrogen atom or a substituent, k represents aninteger of 1 to 5, provided that when k is 2 or more, R₁ may be the samewith or different from each other, and X is the same as defined informula (1), ##STR6## wherein R₃ represents a substituent, R2 and l arethe same as defined in formula (1), provided that when l is 2 or more,R₂ may be the same with or different from each other, and X is the samegroup as defined in formula (1), provided that the group is bonded,through a sulfur atom, to the 4-position of a pyrazolone ring, ##STR7##wherein R₂ and R₃ are the same as defined in formula (2), R₄ representsa substituent, n represents an integer of 1 or 2, provided that when nis 2, R₂ may be the same with or different from each other, and X is ahydrogen atom or the same group as defined in formula (1);

(7) the silver halide photographic material described in any one of (1)through (6), wherein all of the couplers described above aretwo-equivalent couplers;

(8) the silver halide photographic material described in any one of (1)through (7), wherein the light sensitive layer comprises at least twolight sensitive sublayers each containing the couplers described aboveand the sublayers having the same spectral sensitivity;

(9) the silver halide photographic material described in (1), (2) or(3), wherein the light sensitive layer comprises a high-speed lightsensitive sublayer, a medium-speed light sensitive sublayer and alow-speed light sensitive sublayer, which are the same in spectralsensitivity and different in speed; the low-speed sublayer containingdye image forming couplers in an amount that gives a density of not lessthan 40% of the maximum density of the photographic material developed;

(10) the silver halide photographic material described in (1), (2) or(3), wherein the light sensitive layer further contains a DIR compound,the photographic material further comprising a UV-absorbinglight-insensitive layer provided farther from the support than the lightsensitive layer and having a transmission density at a wavelength of 370nm of 1.0 to 2.0 in a minimum density portion;

(11) the silver halide photographic material described in (1), (2) or(3), wherein the light sensitive layer comprises a high-speed lightsensitive sublayer, a medium-speed light sensitive sublayer and alow-speed light sensitive sublayer, which are the same in spectralsensitivity and different in speed, the high-speed, medium-speed andlow-speed sublayers each containing a DIR compound and a molar contentof the DIR compound of the low-speed sublayer being larger than that ofthe high-speed or medium-speed sublayer;

(12) the silver halide photographic material described in any one of (1)through (11), wherein the light sensitive layer contains a coloredcoupler;

(13) the silver halide photographic material described in any one of (1)through (12), wherein the photographic material is a negative film usedin negative-positive process in which a negative image is printed on acolor paper or a monochromatic paper to form a positive print image witha mono-color tone;

(14) a photographing unit, wherein the silver halide photographicmaterial described in (1) through (13) is loaded and packaged in thestate capable of being photographed; and

(15) a method for forming a monochromatic image by exposing the silverhalide photographic material described in any one of (!) through (13)and developing the exposed photographic material with a color developingsolution.

BRIEF EXPLANATION OF THE DRAWING

FIG. 1 is perspective view of a photographing unit.

FIG. 2 is front view of a singlr use camera before being with a papercover.

FIG. 3 is bottom view of a singlr use camera before being provided witha paper cover.

FIG. 4 is exploded perspective view of a camera body, front cover and aback cover.

FIG. 5 is front view of a singlr use camera provided with paper cover.

FIG. 6 is bottom view of a singlr use camera provided with paper cover.

NUMERALS

1 singlr use camera

2 Camera body

3 Front cover

4 Back cover

5 Engaging hole formed on the lower side of back cover 4

6 Engaging protrusion formed on the lower side of camera body

7 Engaging hook formed on the upper side of back cover 4

8 Engaging hole formed on the lower side of back cover 4

11 Engaging protrusion constituting engaging concave formed on the lowerside of back cover 4

12 Engaging hook formed on the lower side of front cover 3

14 Convex portion

15 Finder window

16 Flash window

18 Release button

23 Photographing lens

24 Lens window formed in front cover

28 Flash emitting portion

29 Finder objective lens

30 Carton

31 Lens for photographing

32 Lens mount

33 Stroboscope emitter

34 Finder

35 Pilot lamp of stroboscope charge

36 Film counter window

37 Release button

38 Film winding knob

39 Rear cover

50 Paper cover

51 Notched die-cut line

52 Concave to be put into the edge of paper cover 50

DETAILED DESCRIPTION OF THE INVENTION

In the present invention, the expression "monochromatic" means singlecolor or single color tone, and it is not always to be black-and-whiteor one comprised of developed silver alone. Accordingly, for example, amonochromatic image means an image substantially having a single coloror single color tone.

The relative coupling rate of each of the couplers is determined in theCRR value as defined below. Thus, a photographic material sample whichis prepared through indivisually dispersing the couplers and adding theresulting dispersion into a silver halide emulsion, is exposed anddeveloped in a developing solution. In this case, the maximum density ofthe developed sample is denoted as (Do)_(max). The photographic materialsample is also exposed and developed with the same developing solutionas above, except that citrazinic acid of 1.5 g/l is further added to thedeveloping solution. The maximum density of the developed sample isdenoted as (Dc)_(max). The coupling rate of the coupler can berelatively evaluated, based on the following equation:

    CRR=(Do).sub.max /(Dc).sub.max.

In other words, the CRR value is not less than 1.0 and the closer to1.0, the higher the coupling rate. In cases where plurality of the samecolor type couplers are used in combination, the CRR value of a couplerhaving the highest coupling rate among the couplers is applied.

In general, phenol type cyan couplers having an ureido group at the2-position vary in their reactivity and color tone according to the kindand the amount of a high boiling solvent employed. To obtain amonochromatic image through color development, therefore, yellow,magenta and cyan couplers are preferably contained in identical oildrops so that the relative coupling rate is determined using anidentical high boiling coupler in equal amounts.

According to the invention, the relative rate of coupling of the magentacoupler being higher than that of the yellow or cyan coupler means thatthe CRR value of the magenta coupler is closer to 1.0 than that of theyellow or cyan coupler, and it is preferred that the CRR value of themagenta coupler (denoted as CRR-M), that of the yellow coupler (CRR-Y)and that of the cyan coupler (CRR-C) satisfy the following relationship:

    0.8<CRR-M/CRR-Y<1.0

    0.8<CRR-M/CRR-C<1.0;

Either of CRR-Y and CRR-C may be larger than or equal to the other. Whenthe coupling rate ratio does not fall within the above range, there wereproduced problems such that superior neutrality was not achieved, theyield of finished sepia-toned prints by the printer button operation waslowered, coating was limited due to increased addition of couplers, ortroubles in physical properties such as bleeding occurred, leading tolowering of effects of the invention.

Yellow, magenta and cyan couplers used in the invention include thoseknown in the photographic art.

Next, the coupler represented by formula (1) will be detailed. Informula (1) afore-mentioned, R₁ and R₂ each represent a hydrogen atom ora substituent, k and l each represent an integer of 1 to 5, providedthat when k or l is 2 or more, plural R₁ s or plural R₂ s may be thesame with or different from each other and X represents a group capableof being released when being coupled with an oxidation product of anaromatic primary amine color developing agent to form a dye. Examples ofthe substituent represented by R₁ and R₂ include a halogen atom, andalkyl, cycloalkyl, aryl and heterocyclic groups, which may be bondeddirectly or through a bivalent atom or group. Examples of the bivalentatom or group include oxygen atom, nitrogen atom, sulfur atom,carbonylamino, aminocarbonyl, sulfonylamino, aminosulfonyl, amino,carbonyl, carbonyloxy, oxycarbonyl, ureylene, thioureylene,thiocarbonylamino, sulfonyl, sulfonyloxy, and oxycarbonylamino. Thealkyl, cycloalkyl, aryl and heterocyclic groups cited as examples of thesubstituent represented by R₁ and R₂ may be substituted. Examples ofsubstituents include a halogen atom, nitro, cyano, alkyl, alkenyl,cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryoxycarbonyl,carboxy, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane,sulfonamido, heterocyclic group, arylsulfonyl, alkylsulfonyl, arylthio,alkylthio, alkylamino, anilino, hydroxy, imido, and acyl.

Examples of the group releasable when coupled with an oxidation productof an aromatic primary amine color developing agent to form a dye,represented by X, include a halogen atom, alkoxy, aryloxy,heterocyclic-oxy, acyloxy, alkylthio, arylthio, heterocyclic-thio,##STR8## (in which X₁ represents an atomic group necessary to form a 5-or 6-membered ring containing a nitrogen atom and an atom selected fromthe group of carbon atom, oxygen atom, nitrogen atom and sulfur atom),acylamino, and sulfonamido.

Exemplary examples are shown below.

Halogen atom: chlorine, bromine, iodine atoms

Alkoxy group: ##STR9##

Aryloxy group: ##STR10##

Heterocyclic-oxy group: ##STR11##

Acylthio group: ##STR12##

Alkylthio group: ##STR13##

Arylthio group: ##STR14##

Heterocyclic-thio group: ##STR15## pyrazolyl, imidazolyl, triazolyl,tetrazolyl, ##STR16##

Acylamino group: ##STR17##

Sulfonamido group: ##STR18##

Alkylene group: ##STR19##

In the coupler represented by formula (1) (yellow coupler), X ispreferably aryloxy or ##STR20## (in which X₁ is the same as defined inX1 above-described). Further, the formula (1) includes dimer or higherpolymers which are formed by R₁, R₂ or X.

The coupler represented by formula (2) will be further described below.In formula (2), R₃ represents a substituent, R₂ and l each are the sameas defined in formula (1), provided that when l is 2 or more, plural R₂s may be the same with or different from each other, and X represents agroup which is the same as defined in formula (1), provided that thegroup is bonded, through a nitrogen atom, to the 4-position of apyrazolone ring.

Examples of R₂ include the same groups as exemplified in R₂ of formula(1). Examples of the substituent represented by R₃ alkyl, cycloalkyl,aryl and heterocyclic groups. These groups may be substituted andexamples of substituents include those cited in R₁ and R₂ of formula(1). In couplers (magenta coupler) represented by formula (2), examplesof X include those of formula (1) and preferred thereamong arepyrazolyl, imidazolyl, triazolyl, tetrazolyl and ##STR21## (in which X₁is the same as defined in X₁ above-described). Further, the formula (1)includes dimer or higher polymers which are formed by R₂, R₃ or X.

The coupler represented by formula (3) will be further described below.In formula (3), R₂ and R₃ each are the same as defined in formula (2), prepresents an integer of 1 to 4, provided that when p is 2 or more,plural R₂ s may be the same with or different from each other, and X isa hydrogen atom or the same as defined in formula (1). Examples of R₂and R₃ include those exemplified as R₂ and R₃ of formula (2).

The coupler represented by formula (4) will be further described below.In formula (4), R₂ and l are the same as defined in formula (2),provided that when l is 2 or more, R₂ may be the same with or differentfrom each other, X is the same as defined in formula (1) and Qrepresents a substituent having an ethylenic unsaturated double bond.Examples of R₂ and X include those exemplified in formula (1). Q ispreferably one represented by the following formula (4A): ##STR22##wherein R₄₁ represents a hydrogen atom, a halogen atom, or alkyl(preferably a lower alkyl having 1 to 4 carbon atoms, such as methyl,ethyl and t-butyl), which may be substituted; L represents a bivalentgroup, --CONH--, --NHCONH-- or --NH--; P represent a bivalent group,--CONH--, --SO₂ -- or --COO-- (preferably, --CONH-- or --COO--); Arepresents a bivalent group of alkylene (preferably, alkylene having 1to 10 carbon atoms) or phenylene. The alkylene group may be straightchained or branched, and examples thereof include methylene,methylmethylene, dimethylene and decamethylene and the alkylene andphenylene may be substituted; and m and n each are 0 or 1. In formula(4A) is preferably L of --CONH-- or --NH--, n of 0 or 1, A ofm-phenylene, m of 0 or 1, p of --CONH-- and R₄₁ of lower alkyl; and morepreferably L of --CONH--, m of 0, n of 0 and R₄₁ of a lower alkyl,specifically, methyl. The alkylene and phenylene groups represented by Amay be substituted, and examples of substituents include aryl (e.g.phenyl), nitro, hydroxy, cyano, sulfo, alkoxy (e.g. ethoxy), acyloxy(e.g. acetoxy), acylamino (e.g. acetylamino), sulfonamido (e.g.methanesulfoneamido), sulfamoyl (e.g. methylsulfamoyl), halogen atom(e.g. fluorine, chlorine, bromine), carboxy, carbamoyl (e.g.methylcarbamoyl), alkoxycarbamoyl (e.g. methoxycarbamoyl) and sulfonyl(e.g. methylsulfonyl). The alkylene or phenylene group may besubstituted by two or more of these substituent, in which thesubstituents may be the same with or different from each other. In theinvention is employed a polymer coupler obtained by polymerizing acoupler monomer represented by formula (4). Exemplary examples of thecoupler monomer represented by formula (4) are shown below, but thepresent invention is not limited to these examples. ##STR23##

Exemplary examples of the polymer coupler obtained by polymerizing thecoupler monomer represented by formula (4) are shown below, but thepresent invention is not limited to these examples. ##STR24##

The coupler represented by formula (5) will be further described below.In formula (5), R₁ represents a hydrogen atom or a substituent, krepresents an integer of 1 to 5, provided that when k is 2 or more, R₁may be the same with or different from each other, and X is the same asdefined in formula (1). The formula (5) include diner or higher polymer,which are formed by linking through R₁ or X.

The coupler represented by formula (6) will be further described below.In formula (6), R₃ represents a substituent, R₂ and l are the same asdefined in formula (1), provided that when l is 2 or more, R₂ may be thesame with or different from each other, and X is the same group asdefined in formula (1), provided that the group is bonded, through asulfur atom, to the 4-position of a pyrazolone ring. Examples of R₂include those exemplified as R₂ in formula (1). Examples of R₃ includealkyl, cycloalkyl, aryl and heterocyclic groups. These groups may besubstituted, and examples of substituent include those exemplified asthe substituent in R₁ and R₂ of formula (1). Example of X include thoseexemplified as X in formula (1), and thereamong are preferred alkylthio,arylthio or heterocyclic-thio group. The formula (6) include dimer orhigher polymer, which are formed by linking through R₂, R₃ or X.

The coupler represented by formula (7) will be further described below.In formula (7), R₂ and R₃ are the same as defined in formula (2), R₄represents a substituent, n represents an integer of 1 or 2, providedthat when n is 2, R₂ may be the same with or different from each other,and X is a hydrogen atom or the same group as defined in formula (1).Examples of R₂ and R₃ include those exemplified as R₂ and R₃ in formula(2). Examples of R₄ include those exemplified as R₄ in formula (2). Inthe coupler (cyan coupler) represented by formula (7), example of Xinclude those exemplified as X in formula (1), and thereamong arepreferred a halogen atom, alkoxy, aryloxy and sulfonamido. The formula(7) include dimer or higher polymer, which are formed by linking throughR₂, R₃, R₄ or X.

Exemplary examples of the couplers represented formulas (1) through (3)and (5) through (7) are shown below, but the present invention is notlimited to these examples. ##STR25##

According to the invention, the yellow coupler is incorporatedpreferably in an amount of 5×10⁻⁵ to 2×10⁻³ mol/m², more preferably1×10⁻⁴ to 2×10⁻³ mol/m², and still more preferably 2×10⁻⁴ to 2×10⁻³mol/m² ; the magenta coupler is incorporated preferably in an amount of2×10⁻⁵ to 1×10⁻³ mol/m², more preferably 5×10⁻⁵ to 2×10⁻³ mol/m², andstill more preferably 1×10⁻⁴ to 1×10⁻³ mol/m² ; the cyan coupler isincorporated preferably in an amount of 5×10⁻⁵ to 2×10⁻³ mol/m², morepreferably 1×10⁻⁴ to 2×10⁻³ mol/m², and still more preferably 2×10⁻⁴ to2×10⁻³ mol/m².

To incorporate a coupler used in the invention into a silver halideemulsion, the coupler is dissolved in a high boiling solvent optionallywith a low boiling solvent, mixed with an aqueous gelatin solutioncontaining a surfactant and dispersed by means of a high-speed mixer,colloid mill, ultrasonic homogenizer or capillary tube type dispersingmachine to form an emulsion. Examples of the high boiling solvent usedinclude carboxylic acid esters, carboxylic acid amides, ethers andsubstituted hydrocarbons, such as di-n-butyl phthalate, di-iso-octylphthalate, di-methoxyethyl phthalate, di-n-butyl adipate, di-iso-octyladipate, tri-n-butyl citrate, butyl laurate, di-n-butyl cebacate,tricresyl phosphate, tri-n-butyl phosphate, tri-iso-octyl phosphate,N,N-diethyl caproic acid amide, N,N-dimethylpalmitic acid amide,n-butylpentadecyl phenyl ether, ethyl-2,4-di-tert-butyl phenyl ether,octyl succinate, and dioctyl maleate. Examples of the low boilingsolvent include ethyl acetate, butyl acetate, cyclohexane and butylpropionate.

The silver halide photographic light sensitive material of theinvention, i.e. monochromatic image-forming silver halide photographicmaterial preferably contain a colored coupler. The colored coupler isknown in the photographic art, which has color even in the unreactedstate and which may form dye images such as yellow, magenta, cyan orblack images, or may not form any color image. In general, the coloredcoupler is referred to as one having different colors before and aftercolor development. A colored coupler preferably used in the invention isat least one selected from a yellow-colored magenta coupler, amagenta-colored cyan coupler and a yellow-colored cyan coupler, and willbe further described below.

In the invention, the yellow-colored magenta coupler is referred to as amagenta coupler having an absorption maximum at 400 to 500 nm within thevisible absorption region and capable of forming a magenta dye having anabsorption maximum at 510 to 580 nm within the visible absorptionregion. A yellow-colored magenta coupler preferably used in theinvention is represented by the following formula (I):

    Cp--N═N--R.sub.1                                       formula (I)

wherein Cp represents a magenta coupler moiety, the coupling position ofwhich is bonded to an azo group, and R₁ represents substituted orunsubstituted aryl group. The magenta coupler moiety represented by Cpis preferably one derived from a 5-pyrazolone magenta coupler orpyrazolotriazole type magenta coupler. and more preferably the moietyrepresented by the following formula (II): ##STR26## wherein R₂represents a substituted or unsubstituted aryl group and R₃ representsan acylamino group, anilino group, ureido group or carbamoyl group,which may be substituted. The aryl group represented by R₂ is preferablyphenyl. Examples of substituents for the aryl group include a halogenatom, alkyl (e.g. methyl, ethyl etc.), alkoxy (e.g. methoxy, ethoxyetc.), aryloxy (e.g. phenyloxy, naphthyloxy etc.), acylamino [e.g.benzamido, α-(2,4-di-t-aminophenoxy)butylamido etc.], sulfonylamino(e.g. benzene-sulfonamido, n-hexadecanesulfonamido etc.), sulfamoyl(e.g. methylsulfamoyl, phenylsulfamoyl etc.), carbamoyl (e.g.n-butylcarbamoyl, phenylcarbamoyl etc.), sulfonyl (e.g. methylsulfonyl,n-dodecylsulfonyl etc.), acyloxy, ester group, carboxy, sulfo and nitro.Examples of R₂ include phenyl, 2,4,6-trichlorophenyl, pentachlorophenyl,pentafluorophenyl, 2,4,6-trimethylphenyl, 2-chloro-4,6-dimethylphenyl,2,6-dichloro-4-methylphenyl, 2,4-dichloro-6-methylphenyl,2,4-dichloro-6-methoxyphenyl, 2,6-dichloro-4-methoxyphenyl, and2,6-dichloro-4-[α-(24-di-t-amylphenoxy)acetoamido]phenyl. Examples ofthe acylamino group represented by R₃ include pivaroylamino,n-tetradecaneamido, α-(3-pentadecylphenoxy)-butylamido,3-[α-(2,4-di-t-amylphenoxy)acetoamido]benzamido, benzamido,3-acetoamidobenzamido, 3-(3-n-dodecysuccinamido)-benzamido and3-(4-n-dodecyloxybenzenesulfonamido)benzamido. Examples of the anilinogroup represented by R₃ include anilino, 2-chloroanilino,2,4-dichloroanilino, 2,4-dichloro-5-methoxyanilino, 4-cyanoanilino,2-chloro-5-[α-(2,4-di-t-amylphenoxy)butylamido]anilino,2-chloro-5-(3-octadecenylsuccinimido)anilino,2-chloro-5-n-tetradecaneamidoanilino,2-chloro-5-[α-(3-t-butyl-4-hydroxyphenoxy)tetradecaneamido]anilino and2-chloro-5-n-hexadecanesulfonamidoanilino. Examples of the ureido grouprepresented by R₃ include methylureido, phenylureido and3-[α-(2,4-di-t-amylphenoxy)butylamido]phenylureido. Examples of thecarbamoyl group represented by R₃ include n-tetradecylcarbamoyl, phenylcarbamoyl and 3-[α-(2,4-di-t-amylphenoxy)acetoamido]-phenylcarbamoyl.The aryl group represented by R₁ is preferably phenyl or naphthyl.Examples of substituent for the aryl group represented by R₁ include ahalogen atom, alkyl, alkoxy, aryloxy, hydroxy, acyloxy, carboxy,alkoxycarbonyl, aryloxycarbonyl, alkylthio, arylthio, alkylsulfonyl,arylsulfonyl, acyl, sulfonamido, carbamoyl and sulfamoyl. Of these arepreferred alkyl, hydroxy, alkoxy and acylamino.

Exemplary examples of the yellow-colored magenta coupler represented byformula (I) include YCM-1 to YCM-20 described Japanese PatentApplication No. 8-136765, at page 60-67, but are not limited to these.The yellow-colored magenta coupler preferably used in the invention maybe incorporated into any layer of the photographic material. In caseswhere incorporated into a light sensitive silver halide emulsion layer,the amount to be incorporated is preferably 0.001 to 0.1, morepreferably 0.005 to 0.05, and still more preferably 0.01 to 0.03 mol permol of silver halide.

In the invention, the magenta-colored cyan coupler is referred to as acyan coupler having an absorption maximum at 500 to 600 nm within thevisible absorption region and capable of forming a cyan dye having anabsorption maximum at 630 to 750 nm within the visible absorptionregion. A magenta-colored cyan coupler preferably used in the inventionis represented by the following formula (III): ##STR27## wherein COUPrepresents a cyan coupler moiety, J represents a bivalent linkage, m is0 or 1 and R₅ represents an aryl group.

The cyan coupler moiety represented by COUP is a phenol type cyancoupler moiety and a naphthol type cyan coupler moiety, and preferably anaphthol; type cyan coupler. The bivalent linkage represented by J ispreferably represented by the following formula (IV): ##STR28## whereinY represents ##STR29## R6 represents an alkylene group having 1 to 4carbon atoms or arylene group; R₇ an alkylene group having 1 to 4 carbonatoms, provided that the alkylene group represented by R₆ or R₇ may besubstituted by alkyl, carboxy, hydroxy or sulfo; Z represents --C(R₉)(R₁₀)--, --O--, --S--, --SO--, --SO₂ --, SO₂ NH--, CONH--, --COO--,--NHCO--, NHSO₂ --, or --OCO--, in which R₉ and R₁₀ represent an alkylgroup or an aryl group; R₈ represents an alkyl group, aryl group,heterocyclic group, hydroxy, cyano, nitro, sulfonyl, alkoxy, aryloxy,carboxy, sulfo, halogen atom, carbonamido group, sulfonamido group,carbamoyl group, alkoxycarbonyl or sulfamoyl; p represents 0 or apositive integer; q represents 0 or 1; r represents an integer of 1 to4.

The aryl group represented by R₅ is preferably a phenyl or naphthylgroup, when m is 0. The phenyl and naphthyl groups each may besubstituted by an atom or group, such as a halogen atom, alkoxy,aryloxy, hydroxy, acyloxy, carboxy, alkoxycarbonyl, aryloxycarbonyl,mercapto, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, acyl,acylamino, sulfonamido, carbamoyl and sulfamoyl. When m is 1, the arylgroup represented by R₅ is preferably a naphthol group represented bythe following formula (V): ##STR30## wherein R₁₁ a straight-chained orbranched alkyl having 1 to 4 carbon atoms (e.g. methyl, ethyl, propyl,isopropyl, butyl, s-butyl, t-butyl); and M represents a photographicallyinert cation, including a hydrogen atom, alkaline metal atom such assodium or potassium, ammonium methylammonium, ethylammonium,diethylammonium, triethylammonium, ethanolammonium, diethanolammonium,pyridinium, piperidinium, anilinium, toluidinium, p-nitroanilinium, andanindium. Exemplary examples of the magenta-colored cyan couplerrepresented by formula (III) include MCC-1 through MCC-14, as describedin Japanese Patent Application No. 8-136765 page 71-75, but are notlimited thereto. The magenta-colored cyan coupler preferably used in theinvention may be incorporated into any layer of the photographicmaterial. In cases where incorporated into a light sensitive silverhalide emulsion layer, the amount to be incorporated is preferably 0.001to 0.1, more preferably 0.002 to 0.05, and still more preferably 0.005to 0.03 mol per mol of silver halide.

In the invention, the yellow-colored cyan coupler is referred to as acyan coupler having an absorption maximum at 400 to 500 nm within thevisible absorption region and capable of forming a cyan dye having anabsorption maximum at 630 to 750 nm within the visible absorptionregion. The yellow-colored cyan coupler preferably used in the inventionis represented by the following formula (VI) to (VIII), which ispreferably a cyan coupler capable of releasing, upon coupling reactionwith an oxidation product of an aromatic primary amine developing agent,a compound residue containing an aqueous soluble6-hydroxy-2-pyridine-5-ylazo group, an aqueous solublepyrazolidone-4-ylazo group, aqueous soluble 2-acyaminophenylazo group oraqueous soluble 2-sulfonamido-phenylazo group: ##STR31##

In formulas (VI) to (VIII), Cp represents a cyan coupler moiety, Timerepresents a timing group (which is bonded to the coupling position ofCp), k represents 0 or 1, X represents a bivalent linkage containing N,O or S and linking (Time)_(k) and A, and A represents an arylene groupor a bivalent heterocyclic group.

In formula (VI), R₁₁ and R₁₂ independently represent a hydrogen atom,carboxy, cyano, alkyl, cycloalkyl, aryl, heterocyclic group, carbamoyl,sulfamoyl, carbonamido, sulfonamido or alkylsulfonyl; R₁₃ represents ahydrogen atom, alkyl, cycloalkyl, aryl, or heterocyclic group, providedthat at least one of Time, X, A, R₁₁, R₁₂ and R₁₃ contains aaqueous-solubilizing group (e.g. hydroxy, carboxy, sulfo, ammoniumyl,phosphono, phosphino, hydroxysulfonyloxy, etc.).

In formula (VII), R₁₄ represents acyl or sulfonyl, R₁₅ represents asubstituent, j represents an integer of 0 to 4 and when j is 2 or more,R₁₅ may be the same with or different from each other, provided that atleast one of Time, X, A, R₁₄ and R₁₅ contains a aqueous-solubilizinggroup (e.g. hydroxy, carboxy, sulfo, ammoniumyl, phosphono, phosphino,hydroxysulfonyloxy, etc.).

In formula (VIII), R₁₆ represents a hydrogen atom, carboxy, cyano,alkyl, cycloalkyl, aryl, heterocyclic group, carbamoyl, sulfamoyl,carbonamido, sulfonamido or alkylsulfonyl; R₁₇ represents a hydrogenatom, alkyl, cycloalkyl, aryl, or heterocyclic group, provided that atleast one of Time, X, A, and R₁₆ contains a aqueous-solubilizing group(e.g. hydroxy, carboxy, sulfo, ammoniumyl, phosphono, phosphino,hydroxysulfonyloxy, etc.); and Z represents O or NH.

Exemplary examples of the yellow-colored cyan coupler described aboveinclude YCC-1 through YCC-20, as described in Japanese PatentApplication No. 8-136765 page 76-79, but are not limited thereto. Theyellow-colored cyan coupler preferably used in the invention may beincorporated into any layer of the photographic material. In cases whereincorporated into a light sensitive silver halide emulsion layer, theamount to be incorporated is preferably 0.001 to 0.1, more preferably0.002 to 0.05, and still more preferably 0.005 to 0.03 mol per mol ofsilver halide.

A DIR compound used in the present invention refers to a compoundcapable of releasing a development inhibitor or a precursor thereof uponreaction with an oxidation product of a color developing agent, andthere is preferable used a DIR compound having a releasable developmentinhibitor or its precursor at the active point of a conventionalcoupler. In the invention, the development inhibitor or its precursor ispreferably diffusible one, and diffusible DIR compounds, D-1 throughD-55 are specifically preferred, as defined and exemplified in JP-A4-114153. Exemplary examples of the diffusible DIR compound includethose described in U.S. Pat. No. 3,227,554, 3,647,291, 3,933,500,3,958,993, 4,234,678 and 4,419,886; JP-A 51-13239 and 57-56837; ResearchDisclosure (hereinafter, denoted as RD) 21228 (Dec., 1981).

In the present invention is preferably employed panchromatic-sensitizedsilver halide emulsions, which are sensitive to visible light includingall of blue light, green light and red light. These emulsions can beobtained by blending blue-sensitive, green-sensitive and red-sensitivesilver halide emulsions in a given proportions, or adding, to a singlesilver halide emulsion, blue-sensitizing, green-sensitizing andred-sensitizing dyes to allow the emulsion)s) to be sensitive all ofblue light, green light and red light.

Silver halide grains used in the photographic material according to thepresent invention have specifically no limitation with respect to thesilver halide composition of the interior of the grains. In cases ofsilver iodobromide grains are preferred those having core/shellstructure. The iodide content of the core phase is preferably not lessthan 10 mol % and more preferably not less than 20 mol %. The iodidecontent of the outermost shell layer is preferably not more than 10 mol%, and more preferably not more than 5 mol %. The method for analysis ofsilver halide grains is referred to, for example, one described in JP-A4-142531.

The silver halide emulsion used in the invention is preferably uniformin distribution of the iodide content among grains. When the averageiodide content of each grain is measured, a relative standard deviationof measured values is preferably not more than 20%, more preferably notmore than 15%, and still more preferably between 5 and 12%. Herein, therelative standard deviation is referred to a standard deviation of theiodide content of at least 100 grains, divided by the average iodidecontent times 100.

The silver halide emulsion used in the invention is preferablymonodisperse. The monodisperse silver halide emulsion refers to one inwhich the weight of silver halide grains having grain sizes fallingwithin ±20% of the average grain size account for at least 70%,preferably at least 80% and more preferably 90 to 100% of the totalweight of silver halide. Herein, the average grain size d is defined asa grain size di at the time when the product of frequency ni of thegrain having a size of di and di³, nixdi³ becomes maximum (significantfigure is three digits and the least figure is rounded off). The grainsize is a diameter of a circle with an area equivalent to the projectedarea of the grain. The grain size can be determined by projecting thegrain with expansion of 10,000 to 50,000 times and measuring the graindiameter of the projected area (in which the number of measured grainsis at random 100 or more).

Preferred highly monodisperse emulsion has the width of distribution, asdefined below, of not more than 20%, and more preferably 5 to 15%:

    (Standard deviation of grain size)/(Average grain size)×100=Width of distribution (%)

wherein the grain size can be measured according to the method describedabove, and the average grain size is an arithmetic average, as follow:

    Average grain size=Σdini/Σni.

The average grain size of silver halide emulsion used in the inventionis preferably 0.1 to 10.0 μm, more preferably 0.2 to 5.0 μm, and stillmore preferably 0.3 to 3.0 μm.

The silver halide emulsion preferably contained tabular grains having anaverage aspect ratio of not less than 3, and more preferably of 4 to 20.The average aspect ratio according to the invention can be determined byarithmetically averaging a ratio of the grain size (above-describedequivalent circular diameter) to grain thickness of each emulsion grain,and the concrete definition and the measuring method are the same asdisclosed in JP-A 63-106746, 63-316847 and 2-193138. Further, silverhalide described above is preferably silver iodobromide.

Silver halide emulsions can be prepared using an emulsion preparingapparatus by the double jet method, in which the pAg, pH, temperatureand stirring of the liquid phase during nucleation and growth of silverhalide grains are controlled according to a given pattern, and theaddition of halide(s) such as sodium chloride, potassium bromide andpotassium iodide and silver nitrate is controlled. In the invention,substantially light-insensitive silver halide grains (preferably, finegrain emulsion having an average grain size of 0.01 to 0.2 μm) areeffectively incorporated into a protective layer or an interlayer. Theproportion of the light-insensitive silver halide is preferably 9 to15%, based on the total silver coating weight o the photographicmaterial. Herein, the expression "substantially light-insensitive" meanssensitivity of not more than 1/50 of that of the lowest sensitive grainscontained in a light sensitive emulsion layer.

To achieve broad exposure latitude in the invention, plural silverhalide emulsions different in grain size or halide composition may bemixedly employed, in any ratio, in a single layer. With respect tosilver halide grains different in grain size and mixedly employed ispreferred a combination of silver halide grains having the largestaverage grain size of 0.2 to 2.0 μm and those having the least averagegrain size of 0.05 to 1.0 μm, and silver halide grains having theintermediate average grain size may be further mixed therewith. Theratio of the largest average grain size of silver halide grains to theleast average grain size is preferably 1.5 to 40.

UV absorbents used in the present invention are preferred thosedescribed in JP-A 8-69087. The UV absorbent is incorporated preferablyin an amount of 0.001 to 3 g/m², and more preferably 0.01 to 1.0 g/m².The UV absorbent may be incorporated into any one of photographiccomponent layers, and preferably, for example, a layer nearest to thesupport or a light insensitive layer adjacent thereto, i.e. ananti-halation layer or a backing layer, or a layer farthest from thesupport and on the side nearer to light source or a light insensitivelayer adjacent thereto. According to the invention, it is preferred thata UV absorbing light-insensitive layer, which is provided on the sidefarther from the support, has a transmission density at 370 nm of 1.0 to2.0 in portions corresponding to the minimum density portion on acharacteristic curve. In cases of being less than 1.0, lowering ofcontrast of the monochromatic image occurs, reducing prevention of UVrays produced by static during preparation of the photographic materialand forming so-called static marks. In cases of being more than 2.0, onthe other hand, when monochromatic negative images are printed onblack-and-white print paper, exposure time is extended due to highabsorbance, which is undesirable in terms of working property in thephotofinishing lab. The UV absorbent may be incorporate into aphotographic component layer as it is, if being liquid at ordinarytemperature, or may be dissolved in a low boiling solvent such as ethylacetate, dispersed in an aqueous solution of binder such as gelatin andincorporated into the layer.

The photographic material according to the invention preferablycomprises at least two light sensitive layers, each of which containsplural couplers, that is, a yellow coupler, magenta coupler and a cyancoupler, and which are the same in color sensitivity and different inspeed. Silver halide color photographic materials for use in generalphotography are comprised of at least two light sensitive layers whichare the same in color sensitivity and different in speed, for thepurpose of expanding exposure latitude to enhance photographingallowance. In the present invention was also achieved effects ofenhancing the photographing allowance, and furthermore, according to theinvention, a silver halide monochromatic photographic material which wassuperior in stability of color forming balance and color-developable,was accomplished. The photographic material according to the inventioncomprises more preferably at least three light sensitive layers, each ofwhich contains plural couplers, and which are the same in colorsensitivity and different in speed.

The present invention relates to a silver halide light sensitivemonochromatic photographic material so that its color sensitivity, i.e.spectral sensitivity may basically correspond to the overall region ofspectral luminous efficacy of human eye. Accordingly, as in conventionalsilver halide color photographic materials, it is not necessary toseparate the light sensitive layer into three color sensitive layers andallow couplers different from each other to be contained in each of thelayers, so that even if the light sensitive layer comprises two or morelayers, any color sensitivity of each layer may correspond to overall(panchromatic) region of spectral luminous efficacy of human eye.

According to the invention, contribution of the low speed layer todensity is preferably not less than 40%, and more preferably not lessthan 45%; contribution of the high speed layer to density is preferablynot more than 25%, and more preferably not more than 20%. Sharingrelationship between maximum densities of the low speed layer, mediumspeed layer and high speed layer can be measured according to exposuresystem described in JP-B 7-92597. The high speed layer and medium speedlayer, and the medium speed layer and low speed layer respectively arepreferably adjacent with each other. Each of the high speed layer,medium speed layer and low speed layer is optimized by taking account ofcontrast, graininess and sharpness; it is generally preferred that thehigh speed layer is higher in sensitivity by 0.1 to 1.0 of |logE|(inwhich E is exposure) than that of the medium speed layer, and the mediumspeed layer is higher in sensitivity by 0.1 to 1.0 of |logE| than thatof the low speed layer.

The monochromatic image forming photographic material according to theinvention can achieve the object of the invention through conventionalcolor process comprising the process of developing with a colordeveloping solution after exposure. Preferred examples of theconventional color process include C-41 Process available from EastmanKodak, CNK-4 Process available from Konica, and CN-16 Process availablefrom Fuji Film.

In the invention, monochromatic images can be obtained by printing onblack-and-white print paper or color paper from a color-processedmonochromatic negative film according to the invention, and it ispreferable to obtain a sepia-toned monochromatic image print by printingon color print paper. The sepia-toned color is, in general, lightlydarkish yellow, which is described as 10YR 2.5/2 (color specificationmethod by three attributes) in JIS Z 8721. It is also color belonging toyellow to yellowish red in JIS Z 8701 (color specification method by XYZcolor system and X10Y10Z10 color system). These are described in"Shikisai Kagaku Jiten" (Handbook of Color Science, edited by NihonShikisai Gakkai). In "Iro no Namae Pocket-Zukan" (Kunio Fukuda,published by Shufunotomo), the sepia color is also represented by dotdensities, C60, M74, Y85 and B57 in offset printing.

In the invention, sepia-toned color is defined as the region meeting thefollowing requirements in L*a*b* specification system:

    b*≧a:, b≦3.5a*, 60≦L*≦90, and 5≦c*.

To obtain sepia-toned monochromatic print image by printing on colorprint paper, black-and-white images can be converted to sepia-tonedimages through operating, in printing, e.g. Y-button and C-button,Y-button and M-button, Y-button and M-button, and C-button.

Silver halides used in the invention are not limited and usable arethose described in RD 308119 page 993, item I-A to page 995, item II.Silver halide emulsions which have been subjected to physical ripening,chemical ripening and spectral sensitization, are used. Additives usedin these processes are described in RD17643, page 23, item III to page24, item VI-M; RD18716, pages 648-649; and RD308119, page 996, itemIII-A to page 1000, item VI-M. Known photographic additives used in theinvention are also described in RD17643, page 25, item VIII-A to page27, item XIII; RD18716, pages 650-651; and RD308119, page 1003, itemVIII-A to page 1012, item XXI-E. A variety of couplers are usable in theinvention, and examples thereof are described in RD17643, page 25, itemVII-C to G; RD308119, page 1001, item VII-C to G. The additives used inthe invention can be incorporated through the dispersing methoddescribed in RD308119, page 1007 item XIV. In the invention are usedsupports described in RD17643, page 28 item XVII; RD18716, page 647-648;and RD308119 page 1009, item XVII. There may be provided, in thephotographic material, an auxiliary layer such as a filter layer orinterlayer, described in RD308119, page 1002, item VII-K.

The photographic material according to the invention may be providedwith a magnetic recording layer for inputting various informationsregarding the photographic material such as the kind, production number,name of maker and emulsion number; various informations regardingphotographing such as the photographing date and time, exposure time,illuminating conditions, filter used, climate, photographing size, typeof a camera and use of anamorphic lens; various informations necessaryfor printing such as the number of prints, selection of a filter,favorite color of a client and trimming size; and other informationsregarding the client. The magnetic recording layer is preferablyprovided on the support opposite to photographic component layer(s), anda sublayer, antistatic layer (conductive layer), magnetic recordinglayer and lubricating layer are provided in this order from the support.

One embodiment of the invention is a photographing unit, in which anunexposed photographic material, specifically a monochromatic imageforming photographic material is packaged in the state capable of beingphotographed, and the photographing unit itself need not vary from thatused for a color film and techniques known in the art are applicablethereto. FIG. 1 shows an example of the photographing unit.

The photographic material according to the invention can be loaded in asingle use camera. As a main body of the camera can be employed onedescribed in JP-A 8-76216. Exemplary examples of the main body of thecamera are shown in FIGS. 2 to 5, but are not limited to these. The mainbody of the camera is preferably one having a size of 107×54×26 mm,having a lens of f32 mm and F10, a lens-fitted finder and a shutterspeed of 1/100; or one of 104×54×23 mm, having a lens of f30 mm andf9.5, a lens-fitted finder and a shutter speed of 1/100.

The single use camera is schematically illustrated in FIGS. 2 to 5. Thesingle use camera 1 is comprised of camera body 2, front cover 3 andback cover 4, each of which is formed of resin. An unexposedphotographic film is previously loaded in the camera body 2, the frontcover 3 is attached to the front side of the camera body 2, and the backcover 4 is attached to the back side of the camera body 2. Thus,engaging protrusion 6 formed on the lower side of the camera body 2 isengaged with engaging hole formed on the lower side of back cover 4.Engaging hook 7 formed on the upper side of back cover 4 is engaged withengaging hole 8 formed on the lower side of back cover 3; engagingprotrusion 10 formed on the lower side of front cover 3 is engaged withengaging hole 9 constituting an engaging concave formed on the lowerside of back cover 4, and engaging hook 12 formed on the lower side offront cover 3 is engaged with another engaging hole 11.

Disassembling slot 13 for inserting a tool such as a screw driver isformed on the lower side of back cover 4. Convex portion 14 forbuilding-in a photographing portion is formed in the center of frontcover 3, finder window 15 is formed over convex portion 14, flash window16 is formed in the vicinity of finder window 15, and flash selectionswitch 17 is provide thereunder. Release button 18 is further providedon the upper side of front cover 3.

Single use camera 1 is provided with a paper cover, as shown in FIGS. 5and 6. FIG. 5 is a front view of a single use camera provided with thepaper cover, and FIG. 6 is bottom view thereof. There is provided papercover 50, covering front cover 3 and back cover 4; and paper cover 50,protecting front cover 3 and back cover 4 and explanation for proper useof the camera being described therein. Perforations 51 for easyseparation in disassembling the camera is previously formed on papercover 50, and on the bottom of back cover 3, opposite to the upstream ofperforated line 51, is provided concave portion 52 to be put into theedge portion of paper cover 50. Thereby, it enables easy tearing off ofperforations 51 by allowing fingertips to be put under concave portion52 and pulling the edge of paper cover 50 with fingertips at the time ofdisassembing the camera. In FIG. 6. back cover 4 is provided withconcave portion 52 being positioned under the edge of paper cover 50 andin the case when the upstream side perforations 51 are on positioned onfront cover 3, the front cover 3, concave portion 52 to be put under theedge of paper cover 50 is formed.

EXAMPLES

The present invention is explained further in detail, based on examplesbut embodiments of the invention are not lomited to these examples. Inthe following, unless otherwise noted, the coating amount is representedby g/m², silver halide is represented by equivalent converted to silverand a sensitizing dye is represented by molar number per mol of silverhalide contained in the same layer. In each of silver halideemulsions, agrain size is defined as a diameter of a circle having the areaequivalent to the projected area of the grain, and an average grain sizeand average iodide content (mol %) are shown therein.

EXAMPLE 1

On a transparent, subbed triacetyl cellulose support with a thickness of122 μm were coated layers having the composition as shown below, in thisorder from the support, to prepare a multi-layered monochromaticphotographic material sample 101.

1st Layer: Antihalation layer

    ______________________________________                                        Black colloidal silver                                                                             0.16                                                     UV absorbent (UV-1)  0.25                                                     High boiling organuc solvent (Oil-1)                                                               0.26                                                     High boiling organuc solvent (Oil-2)                                                               0.19                                                     High boiling organuc solvent (Oil-3)                                                               0.58                                                     Colored couplr (CM-1)                                                                              0.26                                                     Colored couplr (CC-1)                                                                              0.10                                                     Gelatin              1.53                                                     ______________________________________                                    

2nd Layer: Interlayer

    ______________________________________                                        Gelatin              0.80                                                     ______________________________________                                    

3rd Layer: Low speed emulsion layer

    ______________________________________                                        Silver iodobromide emulsion A                                                                      0.98                                                     (0.40 μm, 4 mol % iodide)                                                  Sensitizing dye (SD-1)                                                                             7.1 × 10.sup.-5                                    Sensitizing dye (SD-2)                                                                             0.6 × 10.sup.-5                                    Sensitizing dye (SD-3)                                                                             3.4 × 10.sup.-5                                    Sensitizing dye (SD-4)                                                                             8.5 × 10.sup.-4                                    Sensitizing dye (SD-5)                                                                             9.3 × 10.sup.-5                                    Yellow coupler (Y-1) 0.31                                                     Magenta coupler (M-1)                                                                              0.13                                                     Cyan coupler (C-1)   0.28                                                     DIR compound (D-1)   0.03                                                     Antistaining agent (AS-1)                                                                          0.04                                                     High boiling organic solvent (Oil-3)                                                               0.72                                                     Gelatin              2.10                                                     ______________________________________                                    

4th Layer: Medium speed emulsion layer

    ______________________________________                                        Silver iodobromide emulsion B                                                                      1.50                                                     (0.60 μm, 7 mol % iodide)                                                  Sensitizing dye (SD-2)                                                                             1.4 × 10.sup.-5                                    Sensitizing dye (SD-3)                                                                             2.0 × 10.sup.-5                                    Sensitizing dye (SD-6)                                                                             7.9 × 10.sup.-5                                    Sensitizing dye (SD-7)                                                                             5.1 × 10.sup.-5                                    Sensitizing dye (SD-8)                                                                             3.4 × 10.sup.-5                                    Sensitizing dye (SD-9)                                                                             2.7 × 10.sup.-4                                    Yellow coupler (Y-1) 0.23                                                     Magenta coupler (M-1)                                                                              0.12                                                     Cyan coupler (C-1)   0.24                                                     DIR compound (D-2)    0.006                                                   Antistaining agent (AS-1)                                                                          0.03                                                     High boiling organic solvent (Oil-3)                                                               0.55                                                     Gelatin              2.20                                                     ______________________________________                                    

5th Layer: High speed emulsion layer

    ______________________________________                                        Silver iodobromide emulsion C                                                                      1.50                                                     (0.75 μm, 8 mol % iodide)                                                  Sensitizing dye (SD-2)                                                                             0.4 × 10.sup.-5                                    Sensitizing dye (SD-3)                                                                             5.6 × 10.sup.-5                                    Sensitizing dye (SD-6)                                                                             5.5 × 10.sup.-5                                    Sensitizing dye (SD-7)                                                                             6.3 × 10.sup.-5                                    Sensitizing dye (SD-8)                                                                             4.4 × 10.sup.-5                                    Sensitizing dye (SD-9)                                                                             3.2 × 10.sup.-4                                    Yellow coupler (Y-1) 0.12                                                     Magenta coupler (M-1)                                                                              0.07                                                     Cyan coupler (C-1)   0.13                                                     DIR compound (D-2)    0.006                                                   Antistaining agent (AS-1)                                                                          0.02                                                     High boiling organic solvent (Oil-3)                                                               0.33                                                     Gelatin              1.60                                                     ______________________________________                                    

6th Layer: First protective layer

    ______________________________________                                        Silver iodobromide emulsion C                                                                      0.30                                                     (0.05 μm, 3 mol % iodide)                                                  UV absorbent (UV-1)  0.30                                                     Gelatin              1.44                                                     ______________________________________                                    

7th Layer: Second protective layer

    ______________________________________                                        Alkaline-soluble matting agent PM-1                                                                0.15                                                     (average particle size 2 μm)                                               Poly (methyl methacrylate)                                                                         0.04                                                     (average particle size 3 μm)                                               Lubricant (WAX-1)    0.02                                                     Gelatin              0.55                                                     ______________________________________                                    

In addition to the above composition were added coating aids SU-1, SU-2and SU-3, dispersing aid SU-4, viscosity-adjusting agent V-1, stabilizerST-1, dye AI-1, and AI-2, antifoggant AF-1 and AF-2 (two kinds ofpoly(vinyl pyrrolidone) with weight-averaged molecular weight of 10,000and 100,000), hardening agent H-1 and H-2, and anti-septic agent DI-1.

Oill-1: Tricresyl phosphate

Oil-2: Dioctyl phthalate

Oil-3: Dibutyl phthalate

AS-1: 2-Butoxy-5-t-octyl-N,N-dibutylaniline

SU-1: Dioctyl sulfosuccinate sodium salt

SU-2: C₈ H₁₇ SO₂ N(C₃ H₇) CH₂ COOK

SU-3: C₈ H₁₇ SO₂ NH(CH₂)₃ N⁺ (CH₃)₃ ·Br⁻

SU-4: Sodium tri-i-propylnaphthalenesulfonate

St-1: 4-Hydroxy-6-methyl-1,3,3a,7-tetrazaindene

Af-1: 1-phenyl-5-mercaptotetrazole

H-1: 2,4-Dichloro-6-hydroxy-s-triazine sodium salt ##STR32## DI-1(Mixture of the following three components) ##STR33##

Using a combination of couplers as shown in Table 1 and optimallyadjusting the coupler amounts, Samples 102 through 106 were prepared.

Using Samples 101 to 106 and by varying exposure from -4 in a stepedmanner, outdoor portrait photographing was performed and using KonicaMini-lab system NPS-858J-Type II (in which the printer portion was setto print level channel of Konica LV series), photographed samples wereprocessed using process CNK-41-J1 for use in Konica color negative filmand dried to obtain a film sample having monochromatic images. Stabilityof slope with respect to the neutral gray image density was evaluatedfrom monochromatic prints obtained by printing on Konica color papertype QAA5. Sweating was also evaluated as follows.

Evaluation of sweating

Samples 101 to 106 were each conditioned at 55% RH., air-tightlywrapped, and after aging at 70° C. for 3 days, samples were subjected tocolor development processing according to the steps decribed below andthen visually evaluated, based on the following criteria.

x: When held to the light, the sample looked muddy.

Δ: When held to the light, the sample looked slightly muddy.

◯: No abnormality was observed on the surface or in the interior.

Resuts are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________        Coupler in                                                                          Rel. coupling                                                       Sample                                                                            3rd, 4th and                                                                        rate    CRR-M/CRR-Y                                                                           Slope stability with exposure                                                               Sweat-                                No. 5th layers                                                                          Faster  Slower                                                                        CRR-M/CRR-C                                                                           variation (visual evaluation)                                                               ing                                   __________________________________________________________________________    101 Y-1   M-1 > Y-1 > C-1                                                                       0.95    Neutral gray tone was obtained                                                              ◯                         (Inv.)                                                                            M-1           0.94    in the region of low exposure to                        C-1                   high exposure, brilliant black                                                images were obtained.                               102 Y-1   M-2 > C-2 > Y-1                                                                       0.95    Neutral gray tone was obtained                                                              ◯                         (Inv.)                                                                            M-1           0.99    in the region of low exposure to                        C-2                   high exposure, brilliant black                                                images were obtained.                               103 Y-1   M-2 > Y-1 > C-1                                                                       0.91    Neutral gray tone was obtained                                                              ◯                         (Inv.)                                                                            M-2           0.93    in the region of low exposure to                        C-1                   high exposure, brilliant black                                                images were obtained.                               104 Y-2   M-1 > C-1 > Y-2                                                                       0.62    Slightly yellowish-toned images                                                             Δ                               (Inv.)                                                                            M-1           0.94    were obtained in the region of                          C-1                   medium exposure to high                                                       exposure.                                           105 Y-1   M-1 > Y-1 > C-3                                                                       0.95    Slightly bluish-toned images                                                                Δ                               (Inv.)                                                                            M-1           0.57    were obtained in the region of                          C-3                   medium exposure to high                                                       exposure.                                           106 Y-2   M-1 > Y-2 > C-3                                                                       0.62    Slightly reddish-toned images                                                               Δ                               (Inv.)                                                                            M-1           0.57    were obtained in the low density                        C-3                   region.                                             107 Y-1   C-4 > Y-1 > M-3                                                                       1.29    Reddish images were obtained in                                                             ×                               (Comp.)                                                                           M-3           1.46    the overall region.                                     C-4                                                                       __________________________________________________________________________     ##STR34##

Next, in the process of printing work to make up sepia tone-finishedprints by operating the printer-button was made a survey with respect tocomplexity of the operation and stability of the print finish. As aresult, in comparative Sample 104, trial exposure was twice needed toadjust to the printing condition for sepia tone balance, and furtherslight adjustments were needed in some scenes. Contrarily, inventiveSample 101, achieved according to the same condition as in Konica colornegative film LV series. Thus, it was proved to be suited toconventional negative-positive system color photographic process in acommercial processing facility and to be able to stably obtainsepia-toned monochromatic prints without adding any load onto theworking process in a photofinishing laboratory.

Example 2

Samples 201 to 204 were prepared in a manner similar to Sample 101,provided that the coating amount of a coupler, the silver halide grainsize or the extent of chemical sensitization was optimally adjusted sothat the high speed, medium speed and low speed layers each had a sharein density as shown in Table 2 and the contrast in standard colorprocessing (3 min. 15 sec.) had linearity.

Samples were exposed through an optical wedge using 5400K light sourceand processed according to the process described below. Processedsamples were evaluated as follows.

Evaluation of graininess

Graininess of a magenta image was evaluated, based on RMS granularity.RMS granularity was determined by scanning a density of fog plus 0.3with a microdensitometer having an aperture scanning area of 1800 μm²(slit width of 10 μm, slit length of 180 μm) and calculating a 1,000times value of a standard deviation of variation in density of thesampling number of 1,000 or more, and represented as a relative value,based on that of Sample 101 being 100. The less the value, the bettergraininess.

Evaluation of sharpness

Samples were exposed through a pattern used for MTF measurement and aMTF value at 25 cycles/mm was determined. Results are shown in Table 2

                  TABLE 2                                                         ______________________________________                                                 Density share                                                                            Density share                                                      of low speed                                                                             of high speed                                                                             Grain-                                                                              Sharp-                                  Sample No.                                                                             layer (%)  layer (%)   iness ness                                    ______________________________________                                        101 (Inv.)                                                                             45         20          100   0.85                                    201 (Inv.)                                                                             40         25          105   0.82                                    202 (Inv.)                                                                             50         20           95   0.94                                    203 (Comp.)                                                                            30         20          120   0.58                                    204 (Comp.)                                                                            35         35          150   0.62                                    ______________________________________                                    

Furthermore, silver image forming black-and-white photographic material,Konicapan 400 was subjected to standard development in Konicadol DP andmeasured with respect to graininess and sharpness. As a result, it wasproved that inventive Samples 101, 201 and 202 were superior ingraininess and sharpness to Konicapan 400, and comparative Samples 203and 204 were inferior to Konicapan 400.

Processing

    ______________________________________                                        Step         Time        Temperature                                                                             Repl.*                                     ______________________________________                                        Color developing                                                                           3 min.  15 sec. 38 ± 0.3° C.                                                                780 cc                                   Bleaching            45 sec. 38 ± 2.0° C.                                                                150 cc                                   Fixing       1 min.  30 sec. 38 ± 2.0° C.                                                                830 cc                                   Stabilizing          60 sec. 38 ± 5.0° C.                                                                830 cc                                   Drying       1 min.          55 ± 5.0° C.                           ______________________________________                                         *Repl.: Replenishing amount per m.sup.2 of photographic material         

There were employed the following color developer solution, bleachsolution, fixer solution, stabilizer solution, and replenisher solutionsthereof.

Color developer and replenisher solutions

    ______________________________________                                                          Developer   Replenisher                                     ______________________________________                                        Water               800    cc     800   cc                                    Potassium carbonate 30     g      35    g                                     Sodium hydrogencarbonate                                                                          2.5    g      3     g                                     Potassium sulfite   3.0    g      5     g                                     Sodium bromide      1.3    g      0.4   g                                     Potassium iodide    1.2    mg     --                                          Hydroxylamine sulfate                                                                             2.5    g      3.1   g                                     Sodium chloride     0.6    g      --                                          4-Amino-3-methyl-N-ethyl-N-                                                                       4.5    g      6.3   g                                     (β-hydroxyethyl)aniline sulfate                                          Diethylenetriaminepentaacetic acid                                                                3.0    g      3.0   g                                     Potassium hydroxide 1.2    g      2     g                                     ______________________________________                                    

Water was added to make 1 liter, and the pH of developer and itsreplenisher was adjusted to 10.06 and 10.18, respectively, usingpotassium hydroxide or sulfuric acid.

Bleach and replenisher solutions

    ______________________________________                                                         Bleach  Replenisher                                          ______________________________________                                        Water              700 cc    700 cc                                           1,3-Diaminopropanetetraacetic                                                                    125 g     175 g                                            acid iron(III) ammonium salt                                                  Ethylenediaminetetraacetic acid                                                                   2 g       2 g                                             Sodium nitrate      40 g      50 g                                            Ammonium bromide   150 g     200 g                                            Glacial acetic acid                                                                               40 g      56 g                                            ______________________________________                                    

Water was added to make 1 liter, and the pH of bleach and itsreplenisher was adjusted to 4.4 using ammonia water or glacial aceticacid.

Fixer and replenisher solutions

    ______________________________________                                                         Fixer   Replenisher                                          ______________________________________                                        Water              800 cc    800 cc                                           Ammonium thiocyanate                                                                             120 g     150 g                                            Ammonium thiosulfate                                                                             150 g     180 g                                            Sodium sulfite      15 g      20 g                                            Ethylenediaminetetraacetic acid                                                                   2 g       2 g                                             ______________________________________                                    

The pH of the fixer and its replenisher were adjusted to 6.2 and 6.5,respectively with ammonia water or glacial acetic acid, and then waterwas added to each to make 1 liter.

Stabilizer and replenisher solutions

    ______________________________________                                        Water                    900    cc                                            p-Octylphenylpolyoxyethylene ether                                                                     2.0    g                                             Dimethylol urea          0.5    g                                             Hexamethlenetetramine    0.2    g                                             1,2-benzoisothiazoline-3-one                                                                           0.1    g                                             Siloxane (UCC L-77)      0.1    g                                             Ammonia water            0.5    cc                                            ______________________________________                                    

Water was added to make 1 liter, and the pH was adjusted to 8.5 usingammonia water or 50% sulfuric acid.

Example 3

Samples 301 to 307 were prepared in a manner similar to Sample 101,provided that amounts of DIR compounds D-1 and D-2 contained in the 3rd,4th and 5th layers were varied as shown in Table 3.

                  TABLE 3                                                         ______________________________________                                        DIR compound (g/m.sup.2)                                                      Sample No.                                                                            3rd layer (D-1)                                                                            4th layer (D-2)                                                                          5th layer (D-2)                               ______________________________________                                        101 (Inv.)                                                                            0.03         0.006      0.006                                         301 (Comp.)                                                                           0.006        0.03       0.006                                         302 (Comp.)                                                                           0.006        0.006      0.03                                          303 (Inv.)                                                                            0.03         0.012      0.0                                           304 (Inv.)                                                                            0.03         0.0        0.012                                         305 (Comp.)                                                                           0.012        0.03       0.0                                           306 (Comp.)                                                                           0.012        0.0        0.03                                          307 (Inv.)                                                                            0.036        0.006      0.0                                           ______________________________________                                    

Samples 101, 301 to 307 were each exposed and processed in the samemanner as in Example 2 to obtain monochromatic images. The pH of thedeveloper was varied to 9.8 with a diluted sulfuric acid or to 10.4 withan aqueous potassium hydroxide solution. Using each of these developers,samples were similarly processed.

Each of monochromatic images obtained was represented in D-LogEcoordinate system, a straight line with respect to points at the minimumdensity (Dmin)+0.1, Dmin+0.3, Dmin+0.7, Dmin+1.0 and Dmin+1.0 weredetermined by the least square method, and a standard deviation of thedistance between each point and the straight line was determined. Theless the standard deviation, the better linearity. These results areshown in Table 4.

                  TABLE 4                                                         ______________________________________                                                 Standard deviation of                                                         linearity at a pH                                                    Sample No. 9.8           10.06  10.4                                          ______________________________________                                        101 (Inv.) 0.09          0.07   0.08                                          301 (Comp.)                                                                              0.18          0.14   0.17                                          302 (Comp.)                                                                              0.22          0.16   0.20                                          303 (Inv.) 0.10          0.08   0.09                                          304 (Inv.) 0.11          0.09   0.11                                          305 (Comp.)                                                                              0.17          0.11   0.15                                          306 (Comp.)                                                                              0.23          0.17   0.23                                          307 (Inv.) 0.11          0.08   0.10                                          ______________________________________                                    

As can be seen from Table 4, the present invention is not only superiorin linearity at the standard pH but also stable in pH variation.

Example 4

Samples 401 to 404 were prepared in a manner similar to Sample 101,provided that the amount of the UV absorbent in the 6th layer (firstprotective layer) was varied as shown in Table 4. Samples prepared wereeach evaluated with respect to the time for printing on black-and-whiteprint paper and static mark, as follows.

Print time test on black-and-white paper

Samples 101 and 401 to 404 were each subjected to outdoor portraitphotographing and processed according to the steps described above wereperformed. Printing was made through each of the processed samples onblack-and-white paper, Gekko SUPER-VR3 (produced by Mitsubishi SeishiCo.), using an enlarger, Lucky 60M-C (produced by LUCKY Corp.) and at angaperture of 8, and the exposing time was measured.

Evaluation of static mark

The protective layer side of Samples 101, and 401 to 404 were rubbed 20times with a rubber roller positioned in the vicinity of ±0 intriboelectric series to cause static discharge light. Then, samples wereprocessed and evaluated with respect to occurrence of static mark, basedon the following criteria.

A: No occurrence of static mark was observed.

B: Occurrence of static mark was slightly observed.

C: Occurrence of static mark was markedly observed.

                  TABLE 5                                                         ______________________________________                                                          Absorbing                                                            UV       density at                                                                              Print time                                                                           Occurrence of                              Sample No.                                                                             absorbent                                                                              370 nm    (sec.) static mark                                ______________________________________                                        101 (Inv.)                                                                             UV-1     1.5       11     A                                          401 (Inv.)                                                                             UV-1     1.0       11     A                                          402 (Comp.)                                                                            UV-1     0.8       10     B                                          403 (Comp.)                                                                            UV-1     0.5       10     C                                          404 (Comp.)                                                                            UV-1     2.5       22     A                                          ______________________________________                                    

Konicapan 400 was also subjected to outdoor portrait photographing andstandard processing in Konicadol DP. As a result, the print time was 6sec. Accordingly, although the print time is slightly extended,inventive samples were proved to be superior in resistance to staticmark, being provided with function for the system of printing on aconventional color paper and further having suitability toblack-and-white paper.

Example 5

On a transparent, subbed triacetyl cellulose support with a thickness of122 μm were coated layers having the composition as shown below, in thisorder from the support, to prepare a multi-layered monochromaticphotographic material sample 501.

1st Layer: Antihalation layer

    ______________________________________                                        Black colloidal silver                                                                             0.16                                                     UV absorbent (UV-1)  0.21                                                     High boiling organuc solvent (Oil-1)                                                               0.12                                                     Colored couplr (CM-1)                                                                              0.20                                                     Colored couplr (CC-1)                                                                              0.04                                                     Gelatin              1.53                                                     ______________________________________                                    

2nd Layer: Interlayer

    ______________________________________                                        Gelatin              0.80                                                     ______________________________________                                    

3rd Layer: Low speed emulsion layer

    ______________________________________                                        Silver iodobromide emulsion A                                                                      0.98                                                     (0.40 μm, 4 mol % iodide)                                                  Sensitizing dye (SD-1)                                                                             2.4 × 10.sup.-4                                    Sensitizing dye (SD-2)                                                                             2.1 × 10.sup.-4                                    Sensitizing dye (SD-3)                                                                             1.9 × 10.sup.-4                                    Sensitizing dye (SD-4)                                                                             1.7 × 10.sup.-4                                    Yellow coupler (Y-1) 0.26                                                     Magenta coupler (M-1)                                                                              0.21                                                     Cyan coupler (C-1)   0.32                                                     High boiling organic solvent (Oil-2)                                                               0.72                                                     Gelatin              2.10                                                     ______________________________________                                    

4th Layer: Medium speed emulsion layer

    ______________________________________                                        Silver iodobromide emulsion B                                                                      1.50                                                     (0.60 μm, 7 mol % iodide)                                                  Sensitizing dye (SD-1)                                                                             2.3 × 10.sup.-4                                    Sensitizing dye (SD-2)                                                                             1.3 × 10.sup.-4                                    Sensitizing dye (SD-3)                                                                             1.6 × 10.sup.-4                                    Sensitizing dye (SD-4)                                                                             1.3 × 10.sup.-4                                    Yellow coupler (Y-1) 0.20                                                     Magenta coupler (M-1)                                                                              0.16                                                     Cyan coupler (C-1)   0.24                                                     High boiling organic solvent (Oil-2)                                                               0.55                                                     Gelatin              2.20                                                     ______________________________________                                    

5th Layer: High speed emulsion layer

    ______________________________________                                        Silver iodobromide emulsion C                                                                      1.55                                                     (0.75 μm, 8 mol % iodide)                                                  Sensitizing dye (SD-1)                                                                             1.8 × 10.sup.-4                                    Sensitizing dye (SD-2)                                                                             1.0 × 10.sup.-4                                    Sensitizing dye (SD-3)                                                                             1.3 × 10.sup.-4                                    Sensitizing dye (SD-4)                                                                             1.0 × 10.sup.-4                                    Yellow coupler (Y-1) 0.12                                                     Magenta coupler (M-1)                                                                              0.08                                                     Cyan coupler (C-1)   0.16                                                     High boiling organic solvent (Oil-2)                                                               0.33                                                     Gelatin              1.60                                                     ______________________________________                                    

6th Layer: First protective layer

    ______________________________________                                        Silver iodobromide emulsion C                                                                      0.30                                                     (0.05 μm, 3 mol % iodide)                                                  UV absorbent (UV-1)  0.09                                                     UV absorbent (UV-2)  0.10                                                     High boiling solvent (Oil-1)                                                                       0.10                                                     Gelatin              1.44                                                     ______________________________________                                    

7th Layer: Second protective layer

    ______________________________________                                        Alkaline-soluble matting agent PM-1                                                                0.15                                                     (average particle size 2 μm)                                               Poly (methyl methacrylate)                                                                         0.04                                                     (average particle size 3 μm)                                               Lubricant (WAX-1)    0.02                                                     Gelatin              0.55                                                     ______________________________________                                    

In addition to the above composition were added coating aids SU-1, SU-2and SU-3, dispersing aid SU-4, viscosity-adjusting agent V-1, stabilizerST-1, dye AI-1, and AI-2, antifoggant AF-1 and AF-2 (two kinds ofpoly(vinyl pyrrolidone) with weight-averaged molecular weight of 10,000and 100,000), hardening agent H-1 and H-2, and anti-septic agent DI-1.Oil-1 and Oil-2 were dioctyl phthalate and dibutyl phthalate,respectively. ##STR35## DI-1 (Mixture of the following components)##STR36##

Samples 502 to 530 were prepared in the same manner as Sample 501,except that yellow coupler (Y-1), magenta coupler (M-1) or cyan coupler(C-1) was replaced by an equimolar amount of a coupler as shown in thefollowing Table.

                  TABLE 6                                                         ______________________________________                                        Sample Yellow  Magenta  Cyan            CRR-M/                                No.    coupler coupler  coupler                                                                             CRR-M/CRR-Y                                                                             CRR-C                                 ______________________________________                                        501    Y-1     M-1      C-1   0.62      0.91                                  502    1 Y-2   M-1      C-1   0.95      0.91                                  503    Y-1     2 M-2    C-1   0.61      0.90                                  504    Y-1     M-1      3 C-3 0.62      0.99                                  505    Y-1     4 M-2    C-1   0.60      0.89                                  506    1 Y-2   2 M-2    3 C-3 0.93      0.97                                  507    1 Y-3   2 M-2    3 C-3 0.92      0.97                                  598    1 Y-4   2 M-2    3 C-3 0.92      0.97                                  509    1 Y-6   2 M-4    3 C-3 0.93      0.96                                  510    1 Y-6   4 M-2    3 C-3 0.92      0.96                                  511    5 Y-3   2 M-4    3 C-4 0.60      0.91                                  512    1 Y-2   6 M-9    3 C-3 0.91      0.95                                  513    1 Y-3   2 M-4    7 C-7 0.93      0.90                                  514    5 Y-3   6 M-9    7 C-1 0.60      0.93                                  515    5 Y-3   6 M-8    7 C-1 0.61      0.92                                  516    5 Y-4   6 M-9    7 C-1 0.60      0.93                                  517    5 Y-1   6 M-9    7 C-1 0.61      0.93                                  518    5 Y-3   M-1      C-1   0.63      0.91                                  519    1 Y-2   6 M-9    3 C-5 0.91      0.88                                  520    1 Y-2   4 M-2    7 C-7 0.92      0.89                                  521    Y-1     6 M-9    7 C-7 0.59      0.86                                  522    1 Y-2   4 M-6    3 C-3 0.91      0.95                                  523    5 Y-3   4 M-6    7 C-1 0.59      0.93                                  524    5 Y-4   4 M-2    3 C-4 0.61      0.90                                  525    5 Y-3   M-1      7 C-7 0.63      0.90                                  526    5 Y-3   2 M-2    7 C-1 0.60      0.93                                  527    5 Y-3   6 M-8    3 C-3 0.61      0.94                                  528    5 Y-3   M-1      3 C-3 0.63      0.99                                  529    5 Y-3   M-1      7 C-1 0.63      0.94                                  530    Y-1     M-1      7 C-1 0.62      0.94                                  ______________________________________                                    

Samples 501 to 530 were exposed through a wedge used for sensitometryand processed according to the process as in Example 2. The transmissiondensity of each of processed Samples 501 to 530 was measured with amberlight to determine a D-logE curve of monotone images. An intermediatedensity point, which corresponds to an arithmetic average of the maximumand minimum densities of each sample, (which is denoted as normalexposure-point), was defined as standard, and difference in hue wasdetermined with respect to a density point corresponding to 10 times theexposure of the normal exposure-point (which is denoted asoverexposure-point) and a point corresponding to 1/10 of the exposure ofthe normal point (which is denoted as underexposure-point). The huedifference, which is denoted as Z, is an absolute value of the distancebetween a point of a_(x) *b_(y) * represented in terms of CIE1976(L*a*b*) chromaticity coordinate and a point of a₀ *b₀ * at the standardexposure (normal exposure-point), and Z meets the followingrelationship:

    Z=[(a.sub.x *-a.sub.0 *).sup.2 +(b.sub.y *-b.sub.0 *).sup.2 ].sup.1/2

The lower the values at the underexposure-point or theoverexposure-point, the less the hue difference, indicating thatdeviation in color tone from the normal exposure-point as standard isless, and that preferable monotone images having a uniform color-balancein the photographable range from the highlight portion to the shadowportion are formed. Results thereof are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                        Sample  Hue difference Hue difference                                         No.     at underexposure                                                                             at overexposure                                                                          Sweating                                    ______________________________________                                        501     0.8            0.7        Δ                                     502     0.7            0.8        ◯                               503     0.8            0.8        Δ                                     504     0.5            0.5        Δ                                     505     0.8            0.7        Δ                                     506     0.1            0.1        ◯                               507     0.1            0.2        ◯                               508     0.2            0.1        ◯                               509     0.2            0.2        ◯                               510     0.1            0.1        ◯                               511     0.7            0.6        Δ                                     512     0.5            0.4        ◯                               513     0.6            0.5        ◯                               514     0.2            0.1        ◯                               515     0.2            0.2        ◯                               516     0.3            0.1        ◯                               517     0.2            0.2        ◯                               518     0.7            0.5        Δ                                     519     0.6            0.5        ◯                               520     0.6            0.5        ◯                               521     0.5            0.6        Δ                                     522     0.3            0.2        ◯                               523     0.4            0.5        Δ                                     524     0.7            0.5        Δ                                     525     0.6            0.6        Δ                                     526     0.6            0.3        Δ                                     527     0.4            0.5        Δ                                     528     0.5            0.4        Δ                                     529     0.5            0.5        Δ                                     530     0.7            0.4        Δ                                     ______________________________________                                    

As can be seen from Table 7, samples satisfying as a preferableembodiment of the present invention, the combination of couplersrepresented by formulas (1), (2) and (3), the combination of couplersrepresented by formulas (1), (4) and (3), or the combination of couplersrepresented by formulas (5), (6) and (7), were superior in stability ofcolor balance, as compared to other samples. With regard to the slopestability with exposure variation, Samples 502, 506 to 510, 512, 513,519, 520 and 522, which met the following requirements, providedbrilliant black images in the overall region of from low exposure tohigh exposure:

    0.8<CRR-M/CRR-Y<1.0

    0.8<CRR-M/CRR-C<1.0.

Next, using Samples 501 to 530, outdoor portrait photographing wasperformed, and using Konica Mini-lab system NPS-858J-Type II (in whichthe printer portion was set to print level channel of Konica LV series),photographed samples were processed in process CNK-41-J1 for use inKonica color negative film and dried to obtain film samples ofmonochromatic images, 501 to 530. Further, by printing each of them onKonica color paper type QAA5, monochromatic prints were obtained.

In the process of printing to produce sepia-tone finished prints byselecting chices with the printer-button, a survey was done with respectto the complexity of the operation and stability of the print finish. Ascan be seen from Table 7, in samples as a preferable embodiment of thepresent invention, which satisfy the combination of couplers representedby formulas (1), (2) and (3), the combination of couplers represented byformulas (1), (4) and (3), or the combination of couplers represented byformulas (5), (6) and (7), only one trial exposure was needed to adjustthe printing condition for sepia-tone balance; contrarily, in othersamples, sepia-toned color of the highlight portion was different fromthat of the shadow portion, so that several trial exposures were needed.Thus, the present invention was proved to be suitable to conventionalnegative-positive system color photographic process in a commercialprocessing facility and to be able to stably obtain sepia-tonemonochromatic prints without adding anything to the work load in aphotofinishing laboratory.

As shown in the Examples afore-described, the silver halide photographicmaterial according to the invention, i.e., monochromatic image-formingsilver halide photographic material is suited for color photographicprocess of conventional negative-positive system, exhibiting superioreffects such as superior color forming stability and easy printing onprint paper.

What is claimed is:
 1. A silver halide photographic light sensitivematerial comprising a transparent support and provided thereon a lightsensitive layer containing a yellow coupler, a magenta coupler and acyan coupler to form a monochromatic image upon color development afterexposure, wherein a relative rate of coupling of the magenta couplerwith an oxidation product of a color developing agent is greater thanthat of the yellow or cyan coupler;said yellow coupler, said magentacoupler and said cyan coupler being represented by the followingformulas (1), (2) and (3), respectively: ##STR37## wherein R₁ and R₂each represent a hydrogen atom or a substituent; k and l each representan integer of 1 to 5, provided that when k or l is 2 or more, plural R₁s or plural R₂ s may be the same with or different from each other; andX represents a group capable of being released upon coupling with anoxidation product of an aromatic primary amine color developing agent,##STR38## wherein R₃ represents a substituent; R₂ and l each are thesame as defined in formula (1), provided that when l is 2 or more,plural R₂ s may be the same with or different from each other; and Xrepresents the same as defined in formula (1), provided that the groupis bonded, through a nitrogen atom, to the 4-position of a pyrazolonering, ##STR39## wherein R₂ and R₃ are the same as defined in formula(2), p represents an integer of 1 to 4, provided that when p is 2 ormore, plural R₂ s may be the same with or different from each other, andX is a hydrogen atom or the same as defined in formula (1).
 2. Thesilver halide photographic material of claim 1, wherein the relativecoupling rate of the yellow, magenta or cyan coupler is defined in termof the following CRR value, said CRR value of the magenta coupler beingless than that of the yellow or cyan coupler:

    CRR=(Do).sub.max /(Dc).sub.max

wherein (Do)_(max) represents a maximum density obtained when aphotographic material sample that contains singly the yellow, magenta orcyan coupler is subjected to exposure and color development in adeveloping solution, and (Dc)_(max) represents a maximum densityobtained when the photographic material sample is subjected to exposureand development in the developing solution that further containscitrazinic acid of 1.5 g/l.
 3. The silver halide photographic materialof claim 2, wherein a CRR value of the magenta coupler (CRR-M), that ofthe yellow coupler (CRR-Y) and that of the cyan coupler (CRR-C) satisfythe following relationship,

    0.8<CRR-M/CRR-Y<1.0

    0.8<CRR-M/CRR-C<1.0.


4. 4. The silver halide photographic material of claim 1, wherein saidyellow coupler, said magenta coupler and said cyan coupler each are atwo-equivalent coupler.
 5. The silver halide photographic material ofclaim 1, wherein said light sensitive layer comprises at least two lightsensitive sublayers, said two sublayers each containing the couplers asclaimed in claim 1 and having the same spectral sensitivity.
 6. Thesilver halide photographic material of claim 1, wherein said lightsensitive layer comprises a high-speed light sensitive sublayer, amedium-speed light sensitive sublayer and a low-speed light sensitivesublayer, which are the same in spectral sensitivity and different inspeed; said sublayers each containing the couplers as claimed in claim 1and said low-speed sublayer containing couplers in an amount that givesa density of not less than 40% of the maximum density of thephotographic material developed.
 7. The silver halide photographicmaterial of claim 1, wherein said light sensitive layer further containsa DIR compound, the photographic material further comprising aUV-absorbing light-insensitive layer provided farther from the supportthan said light sensitive layer, and said UV-absorbing layer having atransmission density at a wavelength of 370 nm of 1.0 to 2.0 in aminimum density portion.
 8. The silver halide photographic material ofclaim 1, wherein said light sensitive layer comprises a high-speed lightsensitive sublayer, a medium-speed light sensitive sublayer and alow-speed light sensitive sublayer, which are the same in spectralsensitivity and different in speed; said high-speed, medium-speed andlow-speed sublayers each containing the couplers as claimed in claim 1and further containing a DIR compound, a molar content of the DIRcompound of said low-speed sublayer being larger than that of saidhigh-speed sublayer or medium-speed sublayer.
 9. The silver halidephotographic material claim 1, wherein said light sensitive layercontains a colored coupler.
 10. The silver halide photographic materialof claim 1, wherein said photographic material is a negative film usedin negative-positive process in which a negative image is printed on acolor paper or a monochromatic paper to form a positive print image witha mono-color tone.
 11. A silver halide photographic material whereinsaid yellow coupler, said magenta coupler and said cyan coupler arerepresented by the following formulas (5), (6) and (7), respectively,##STR40## wherein R₁ represents a hydrogen atom or a substituent; krepresents an integer of 1 to 5, provided that when k is 2 or more,plural R₁ 's may be the same as or different from each other; and X is agroup capable of being released upon coupling with an oxidation productof an aromatic primary amine color developing agent; ##STR41## whereinR₃ represents a substituent; R₂ is hydrogen or a substituent and l is aninteger of 1 to 5, provided that when l is 2 or more, plural R₂ 's maybe the same as or different from each other; and X is the group asdefined in formula (5), provided that the group is bonded, through asulfur atom, to the 4-position of a pyrazolone ring, ##STR42## whereinR₂ and R₃ are the same as defined in formula (6); R₄ represents asubstituent; n represents an integer of 1 or 2, provided that when n is2, plural R₂ 's may be the same as or different from each other; and Xis a hydrogen atom or the same as defined in formula (5).
 12. A silverhalide photographic light-sensitive material comprising a transparentsupport and provided thereon a light-sensitive layer containing a yellowcoupler, a magenta coupler and a cyan coupler to form a monochromaticimage upon color development after exposure, wherein a relative rate ofcoupling of the magenta coupler with an oxidation product of a colordeveloping agent is greater than that of the yellow or cyan coupler;saidyellow coupler, and said cyan coupler being represented by the followingformulas (1) and (3), respectively; and said magenta coupler obtained bypolymerization of a monomer represented by formula (4): ##STR43##wherein R₁ and R₂ each represent a hydrogen atom or a substituent; k andl each represent an integer of 1 to 5, provided that when k or l is 2 ormore, plural R₁ 's or plural R₂ 's may be the same with or differentfrom each other; and X represents a group capable of being released uponcoupling with an oxidation product of an aromatic primary amine colordeveloping agent, ##STR44## wherein R₂ and R₃ are the same as defined informula (2), p represents an integer of 1 to 4, provided that when p is2 or more, plural R₂ 's may be the same or different from each other,and X is a hydrogen atom or the same as defined in formula (1),##STR45## wherein R₂ and I are the same as defined in formula (1),provided that when I is 2 or more, plural R₂ 's may be the same ordifferent; X is as defined in formula (1); and Q represents asubstituent having an ethylenic unsaturated double bond.